With the conventional Haber–Bosch NH₃ synthesis in industry requiring harsh pressures and high temperatures, artificial N₂ fixation has been long sought after. The electrochemical nitrogen reduction reaction (NRR) could offer a solution by allowing NH₃ production under ambient conditions. In this review, important recent findings on theoretical calculations and experimental exploration on the NRR at room temperature are systematically reviewed. Firstly, we discuss the mechanism of electrochemical heterogeneous catalysis for the NRR. The NRR is a multi-proton coupled electron transfer (PCET) process which implies that in addition to catalyst surface size effects, ligand and strain effects will also significantly influence the binding energy of the adsorbed N atoms, reaction intermediates and product species. Electrocatalysts including metals, metal nitrides, metal oxides and carbon-based materials will also be discussed at length. A linear scaling relationship seems to limit the NRR activity on most metals and metal oxides. Metal nitrides, however, follow the Mars–van Krevelen (MvK) mechanism which usually shows a lower potential energy barrier compared to the associative mechanism. Carbon-based materials and some single atom catalysts exhibit improved activity and selectivity due to ligand effects. Thus, electrolytes containing a proton donor might play a crucial role in the NRR. The limiting concentration of proton donors and the rate of proton transport to the active sites might be effective factors in boosting the selectivity of the NRR. Specifically, ionic liquids with high N₂ solubility demonstrate much larger faradaic efficiency and would be promising candidates for use in NRR processes. Inspired by the characteristics of PCET, four strategies of electrode engineering were introduced including limiting protons, tuning the electron transport, modifying the electrode structure facilitating mass transport, and completely changing the NRR mechanism inspired by bio-nitrogenase and Li mediated N₂ fixation.